Surfactant triazine compounds and their use

ABSTRACT

Polymeric, water-soluble triazine compounds which contain both basic and acidic groups in the molecule have out-standing surfactant properties and are suitable for the preparation of dispersions of solids, preferably of dispersions of inorganic and/or organic pigments, in an aqueous or water-dilutable medium. Since these triazine compounds are colorless or only slightly colored, they do not influence the shade of the medium used.

The present invention relates to the technical area of the surfactantcompounds.

The triazine compounds mainly used at present in industry are cropprotection agents, melamine resins and especially textile dyes. Suchcompounds are, as a rule, composed of a triazine ring, sometimes twotriazine rings, which are substituted by chromophores. In general, thesedyes are rendered water-soluble by substituents on the chromophores. Toinfluence the tinctorial properties, the triazine ring may carry furthersubstituents, for example amino groups having aliphatic radicals,vinylsulfonyl groups and alkoxy groups. Such compounds are used fordyeing textile materials. Oligomeric and polymeric triazine compoundswhich are composed of more than two triazine rings are also known. U.S.Pat. No. 4,314,001 and U.S. Pat. No. 4,347,352 describe polymerictriazine compounds of the general formula I (see formulae), in which Yand Z are substituents containing amino groups, which compounds aresuitable as mordants for water-soluble dyes on cellulose, as fixingagents for pigments on cellulose or as surfactants for aqueous pigmentdispersions. U.S. Pat. No. 3,622,339 likewise mentions polymerictriazine compounds of the general formula II (see formulae), in which R¹is a radical containing amino, hydroxyalkyl or mercapto groups, R², R³,R⁴ and R⁵ are each hydrogen or an alkyl group and Y¹ and Y² are each anunsubstituted or substituted alkylene or arylene diradical, whichcompounds are used as antifogging agents in film emulsions. U.S. Pat.No. 4,228,281 describes dicarboxylic acids which contain polymerictriazine rings and are of the general formula III (see formulae), inwhich R¹, R² , R³ and R⁵ are each hydrogen or a C₁ -C₂₂ -alkylhydrocarbon radical, R⁴ is a C₂ -C₁₈ -hydrocarbon diradical and R⁶ is aC₁ -C₁₂ -hydrocarbon diradical, which acids are used for the synthesisof polyesters having a glass transition temperature above 100° C.

It is the object of the present invention to provide polymericwater-soluble triazine compounds which are colorless or only slightlycolored, have good surfactant properties and may also be suitable forpigmenting or for coating the surface of pigments. The object isachieved by a novel class of triazine compounds which contain basic andacidic groups and are of the general formula IV (see formulae), in whichX is a group of the formula IVa (see formulae), in which A¹ is a bridgemember selected from the group comprising O, S or NR³, wherein R³ ishydrogen or a C₁ -C₂₂ -alkyl radical or a C₃ -C₂₂ -alkenyl radical,preferably a C₁ -C₄ -alkyl radical or hydrogen, in particular methyl orhydrogen, which is unsubstituted or substituted by an OH group, D¹ is anarylene group or a branched or straight-chain C₂ -C₁₂ -alkylene group,which may be interrupted by one or more bridge members selected from thegroup A², and A², independently of A¹, is selected from the same groupof substituents as A¹, and R¹ and R², independently of one another, arebranched or straight-chain C₁ -C₂₀ -alkyl groups or C₂ -C₂₀ -alkenylgroups, preferably C₁ -C₆ -alkyl groups, or in which R¹ and R², togetherwith the nitrogen atom, form an unsaturated or saturated five- orsix-membered ring which may additionally contain one or two nitrogen,oxygen and/or sulfur atoms as further hetero atoms in the ring, or inwhich X is a group of the formula IVb (see formulae), wherein R⁴ is C₁-C₆ -alkyl and Y¹ and Y², independently of one another are each a groupof the formula IVc (sec formulae), in which A³ is independent of A¹ andis a bridge member selected from the same group of substituents as A¹,D² is independent of D¹ and is selected from the same group ofsubstituents as D¹ or is CH₂ or a direct bond, and E¹ is ananion-forming group, preferably COOM, SO₃ M, OSO₃ M or OPO₃ M₂, in whichM is hydrogen, a metal, in particular an alkali metal or thestoichiometric amount of an alkaline earth metal, or an ammonium ionwhich is unsubstituted or substituted by aliphatic, aromatic andaraliphatic radicals, and Z is a group of the formula IVd (seeformulae), in which A⁴ is independent of A¹ and is a bridge memberselected from the same group of substituents as A¹ and Z* is the groupCO, branched or straight-chain C₂ -C₂₅ -alkylene, C₅ -C₆ -cycloalkyleneor C₆ -C₁₄ -arylene, preferably C₂ -C₆ -alkylene or phenylene, which isunsubstituted or substituted by COOM, SO₃ M, Cl, OH or alkoxy groups,wherein M has the abovementioned meanings and wherein, in the cycliccompounds, some of the carbon atoms may be replaced by the hetero atomsnitrogen, oxygen and/or sulfur, or wherein Z is a bridge member of thegeneral formulae IVe and IVf (see formulae), in which A⁵ is a group ofthe formula CR⁵ R⁶, NR⁷, O, SO, SO₂ or CO, preferably CR⁵ R⁶, NR⁷ or O,in which R⁵ and R⁶, independently of one another, may be branched orstraight-chain C₁ -C₄ -alkyl groups or hydrogen, and in which R⁷,independently of R³, is selected from the same group of substituents asR³, or Z is any combination of groups of the formulae IVd, IVe and/orIVf, and m is an integer of from 1 to 100.

Preferred compounds of the general formula IV (see formulae) are thosein which X is a group of the formula IVa (see formulae), in which A¹ isa bridge member selected from the group comprising O and NR³, in whichR³ is hydrogen or a C₁ -C₂₂ -alkyl radical or a C₃ -C₂₂ -alkenylradical, preferably a C₁ -C₄ -alkyl radical or hydrogen, in particularmethyl or hydrogen, which is unsubstituted or substituted by an OHgroup, D¹ is an arylene group or a branched or straight-chain C₂ -C₁₂-alkylene group which may be interrupted by one or more bridge membersselected from the group A², and A², independently of A¹, is selectedfrom the same group of substituents as A¹, and R¹ and R², independentlyof one another are branched or straight-chain C₁ -C₂₀ -alkyl groups orC₃ -C₂₀ -alkenyl groups, preferably C₁ -C₆ -alkyl groups, or in which R¹and R² , together with the nitrogen atom, form an unsaturated orsaturated five- or six-membered ring which may additionally contain oneor two nitrogen or oxygen atoms as further hetero atoms in the ring, orin which X is a group of the formula IVb (see formulae), wherein R⁴ isC₁ -C₆ -alkyl, and Y¹ and Y², independently of one another are each agroup of the formula IVc (see formulae), in which A³ is independent ofA¹ and is a bridge member selected from the same group of substituentsas A¹, D² is independent of D¹ and is selected from the same group ofsubstituents as D¹, or is CH₂ or a direct bond, and E¹ is ananion-forming group, preferably COOM or SO₃ M, wherein M is hydrogen, ametal, in particular an alkali metal or the stoichiometric amount of analkaline earth metal, or an ammonium ion, which is unsubstituted orsubstituted by aliphatic, aromatic or araliphatic radicals, and Z is agroup of the formula IVd (see formulae), in which A⁴ is independent ofA¹ and is a bridge member selected from the same group of substituentsas A¹, and Z* is the group CO, NR³, in which R³ has the abovementionedmeaning, branched or straight-chain C₂ C₂₅ -alkylene, C₅ -C₆-cycloalkylene or phenylene, preferably C₂ -C₆ -alkylene or phenylene,which is unsubstituted or substituted by COOM or SO₃ M, in which M hasthe abovementioned meanings, and wherein, in the cyclic compounds, someof the carbon atoms may be replaced by the hetero atoms nitrogen and/oroxygen, or Z is a combination of the groups of the formula IVd, and m isan integer of from 1 to 100.

Particularly preferred compounds of the general formula IV (seeformulae) are those in which X is a group of the formula IVg (seeformulae), in which R⁸ is methyl or hydrogen, and D¹ is a branched orstraight-chain C₂ -C₆ -alkylene group or a phenylene group, and R¹ andR² are independently of one another branched or straight-chain C₁ -C₆-alkyl groups, or in which R¹ and R², together with the nitrogen atom,form an unsaturated or saturated five-or six-membered ring which mayadditionally contain one or two nitrogen and/or oxygen atoms as furtherhetero atoms in the ring, and Y¹ and Y², independently of one anotherare each a group of the formula IVh (see formulae), in which R⁹ isindependent of R⁸ and is a substituent selected from the same group asR⁸, and D² is independent of D¹ and is selected from the same group ofsubstituents as D¹ or is CH₂ or a direct bond, and E¹ is ananion-forming group, preferably COOM or SO₃ M, wherein M is hydrogen, ametal, in particular an alkali metal or the stoichiometric amount of analkaline earth metal, or an ammonium ion, which is unsubstituted orsubstituted by aliphatic, aromatic and araliphatic radicals, and Z is agroup of the formula IVi (see formulae), in which R¹⁰ is methyl orhydrogen, and Z* is the group C₂ -C₆ -alkylene or phenylene, which isunsubstituted or substituted by COOM or SO₃ M, wherein M has theabovementioned meanings, or in which Z* is a group of the formula IVj(see formulae), in which Z** is the group N-C₁ -C₂₀ -alkyl, NH or O, andm is an integer of from 1 to 30.

The compounds according to the invention are colorless or only slightlycolored, which enables them to be used widely in the area of surfactantsubstances, since they do not influence the shade of the medium in whichthey are used.

According to the prior art, triazine compounds are synthesized by anucleophilic substitution of the halogen atoms in cyanuric halides, inparticular cyanuric chloride, by amine, hydroxy or mercapto derivativesat temperatures of -10° to +200° C. (J. Am. Chem. Soc. Vol. 73 (1951),2981-2996). The substitution reaction can be selectively controlled bytemperature control and pH monitoring, which is carried out by means ofacid acceptors, such as, for example, sodium hydroxide solution orsodium carbonate. Substitution of all three halogen atoms with differentradicals can be carried out in succession in a single reaction vessel.However, this process is not applicable to the compounds according tothe invention, since Y¹ and Y² can be introduced only with the randomdistribution thereby. If the reactivities of Y¹ -H and Y² -H differgreatly from one another, it is possible that only Y¹ or Y² issubstitutable. The products of the general formula IV in which Y¹ =Y²,which are formed in the synthesis in a single reaction vessel, possessphysical and chemical properties which are not very suitable for theintended application.

The present invention furthermore relates to a process for the synthesisof a compound of the general formula IV, wherein, in separatecontainers, first a compound of the formula Y¹ -H (first reaction batch)and one of the formula Y² -H (second reaction batch) are each reacted inaqueous solution with a cyanuric halide, preferably cyanuric chloride,at a temperature of 0° to 10° C., preferably 0° to 5° C., then theintermediate formed in the reaction batch is reacted with a compound ofthe formula X-H and the intermediate formed in the second reaction batchis reacted with a compound of the formula ZH₂, in each case at atemperature of from 20° to 60° C., preferably 35° to 45° C., and the tworeaction batches are then combined and are reacted with 0.1 to 0.6 molof ZH₂ per mol of cyanuric halide used, at a temperature of 70° to 150°C., preferably 75° to 95° C.

As a result of this reaction procedure, the two terminal triazine ringseach contain the acidic group Y¹ and the substituent X having a basicfunction, in particular a tertiary nitrogen atom, while all othertriazine rings are substituted by the acidic group Y². The synthesis iscarried out in two separate reaction vessels, the reaction preferablybeing carried out in water as a solvent, to which small amounts of asurfactant, for example a sulfonated fatty acid derivative, have beenadded.

In the first step, the groups Y¹ or Y² are bonded to the cyanuric halidein water in separate stirred vessels (A) and (B). For this purpose, 0.8to 1.2 mol of Y¹ -H or Y² -H are used per mol of cyanuric halide, andthe reaction is carried out at 0° to 10° C., preferably 0° to 5° C. Inan idealized form, the reactions take place according to reaction scheme1 (see formulae).

In the second step, the group X in reaction vessel (A) (reaction productV) on the one hand and the group Z in reaction vessel (B) (reactionproduct VI) on the other hand are substituted at 20° to 60° C.,preferably 35° to 45° C. (reaction scheme 2, see formulae). In thisstep, 0.8 to 1.2 mol of X-H or 0.3 to 1.2 mol of H-Z-H are used in eachcase per mol of cyanuric halide. Thereafter, the two resultingintermediates VII and VIII are bonded via Z at 70° to 150° C.,preferably 75° to 95° C., 0.1 to 0.6 mol of H-Z-H being used per mol ofcyanuric halide (reaction scheme 3, see formulae). This amount of H-Z-Hmay advantageously also be present in the reaction of VI to give VIII.

To neutralize the acid HHal formed in the reaction, an acid acceptor,for example sodium hydroxide solution or potassium hydroxide solution,sodium carbonate, sodium bicarbonate or potassium carbonate, is added ineach reaction stage, gradually as the reaction progresses (decrease inpH) or all at once, in an amount such that the pH of the reactionmixtures is 6 to 9. The reaction mixture obtained in this manner can beused directly for the applications according to the invention, ifnecessary after any solid constituents present have been filtered off.Furthermore, the reaction product can be precipitated from the solutionby adding acids, for example hydrochloric acid or sulfuric acid, andseparated off by filtration. The solvent can be removed from thereaction mixture by means of a vacuum, elevated temperature or spraydrying, and the resulting salt can be removed by adding organicsolvents, preferably dimethyl sulfoxide. The salt can also be separatedoff by membrane separation methods.

After precipitation by means of an acid, the product can be used as asurfactant in the form of the still moist press cake, in a dry form andin the form of an amine, alkali metal salt or alkaline earth metal saltsolution. Examples of amines for salt formation are: methylamine, mono-,di- and triethylamine, mono-, di- and triethanolamine,dimethylethanolamine, methyldiethanolamine anddimethylaminomethylpropanol.

Examples of the compounds of the formula X-H areN,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine,aminobenzyldimethylamine, 2-dimethylaminoethylamine,3-diethylaminopropylamine, 3-dimethylaminopropylamine, N¹,N¹-diethyl-1,4-pentanediamine, N,N-dimethylneopentanediamine,2-pyrrolidinoethylamine, N-(3-aminopropyl)-imidazole,dimethylneopentanolamine or 4-dimethylamino-1-butanol.

Examples of the compounds of the formulae Y¹ -H and Y² -H are o-, m- andp-aminobenzoic acid, o-, m- and p-aminobenzenesulfonic acid, glycine,alanine, β-alanine, 4-aminobutyric acid, amidosulfonic acid,2-aminoethanesulfonic acid, o-, m- and p-hydroxybenzoic acid,phenolsulfonic acid, 6-hydroxycaproic acid, 5-hydroxyvaleric acid,4-hydroxybutyric acid, 4-hydroxy-1-butanesulfonic acid,hydroxynaphthalenesulfonic acid, hydroxypivalic acid or mercaptoaceticacid.

Examples of the compounds of the formulae ZH₂ are 1,2-diaminoethane,1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane,1,6-diaminohexane, 1,8-diaminooctane,1,12-diaminododecane,neopentanediamine,3,6-dioxaoctane-1,8-diamine,4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine,4,7,10-trioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine,4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane,N-(2-aminoethyl)-1,2-ethanediamine,N-(2-aminopropyl)-1,3-propanediamine, 4,4'-diaminodiphenyl ether,4-amino-N-(4-aminophenyl)-benzenesulfonamide, 4,4'-diaminobenzanilide,1,4-phenylenediamine-2-sulfonic acid, 4,4'-dihydroxydiphenyl sulfone oro-, m- and p-dihydroxybenzene.

The compounds according to the invention of the general formula IV arein the protonated form, in the form of the zwitter ion or in thedeprotonated form, depending on the pH.

The compounds according to the invention are in general readily solublein polar and in protic solvents, if necessary at elevated pH. Thesurfactant properties of the compounds according to the invention areevident, for example, in the reduction of the surface tension of anaqueous solution. This can be determined by the ring tear method (DIN53,914) and, depending on the compound, gives values of 35 to 45 mN/m ata measurement temperature of 25° C. in aqueous amine-alkaline solution(pH 9.0) (comparative value of an aqueous amine-alkaline solution at pH9.0:70 mN/m).

The compounds according to the invention are suitable as dispersants,emulsifiers and distributing agents for solids in aqueous media. Thepresent invention therefore also relates to the use of the compoundsaccording to the invention as surfactants and as dispersants,emulsifiers or distributing agents for solids in aqueous media. Inparticular, the compounds according to the invention can be used indispersions which contain, as solids, for example minerals, cropprotection agents and pesticides, dyes, pigments and opticalbrighteners. Furthermore, the compounds according to the invention aresuitable as dyeing assistants and stabilizers, for the wet-end coloringof regenerated cellulose and as dispersants for aqueous flexographicprinting. The suitability of the compounds according to the inventionfor the production of highly pigmented, free-flowing pigmentpreparations of inorganic and organic pigments, such as, for example,azo pigments, quinacridones, flavanthrone, anthanthrone and pyranthronepigments, derivatives of naphthalenetetracarboxylic acid and ofperylenetetracarboxylic acid, of thioindigo, of dioxazine, of theisoindolines, of the isoindolinones and of the diketopyrrolopyrroles,laked pigments, such as the magnesium, calcium, strontium, barium,aluminum, manganese and nickel lakes of dyes containing acid groups, ofphthalocyanine pigments and of corresponding pigment mixtures must beparticularly emphasized. The abovementioned pigment preparations areunderstood as meaning on the one hand pigment dispersions inconcentrated form which can be converted into the final lake formulationby dilution with binders based on aqueous polyacrylate, polyester andpolyurethane systems and on the other hand pigment preparations whichare incorporated in powder form into the medium used.

The invention thus relates to pigment dispersions essentially containingat least one of the compounds of the formula IV and at least oneinorganic and/or organic, preferably polycyclic, pigment. The inventionfurthermore relates to pigment preparations of organic, preferablypolycyclic, pigments, in particular of perylene and dioxazine pigmentsand of quinacridones. The compounds according to the invention, of theformula IV, can be used individually or as a mixture and also incombination with other nonionic, anionic or cationic surfactants ormixtures thereof. They can also be used together with builders or otherconventional additives or assistants. The composition of the statedpigment preparations can vary within wide limits.

The preferred pigment preparation essentially consists of

a) 99.5 to 50% by weight, preferably 97 to 70% by weight, of at leastone organic, preferably polycyclic, pigment,

b) 0.5 to 30% by weight, preferably 3 to 20% by weight, of at least onecompound of the formula IV and

c) 0 to 20% by weight, preferably 0 to 10% by weight, of furtherconventional additives, for example foam regulators and viscosityregulators, surfactants, sedimentation inhibitors, wetting agents andpreservatives.

The present invention also relates to a process for the preparation ofthe pigment preparations, wherein the surface of the pigments is coatedwith at least one of the compounds of the formula IV. Depending on theembodiment, application of these compounds to the pigment particles maybe effected either in aqueous suspension, in organic solvents or inmixtures of water or organic solvents. There are a number ofpossibilities for applying the compounds according to the invention tothe pigment surface. This may be carried out during or after the pigmentsynthesis or during or after a finish process. Compounds of the formulaIV can also be added during incorporation of the pigments into themedium used. When the compounds according to the invention are appliedto the pigment surface in aqueous suspension or in water/solventmixtures, the pigment is then usually isolated by filtration. As a rule,the pH has an effect on the pigment properties. A pH of 7 to 12,particularly preferably 7.5 to 9, is preferred.

The invention also relates to the use of the pigment dispersions andpigment preparations according to the invention for pigmenting andcoloring natural and synthetic materials. A preferred use is for thepreparation of aqueous coatings, emulsion paints and printing inks. Theuse of the pigment preparations and of the pigment dispersions forpigmenting aqueous coating systems is particularly preferred. In allconventional aqueous binder systems, such as polyacrylates,polyurethanes and polyesters, the pigment preparations and pigmentdispersions according to the invention give pure brilliant shades withhigh color strength and high transparency. The pigment pastes have goodrheological properties in conjunction with high pigment contents andconstant pH, even after storage at elevated temperatures for severalweeks. For testing the suitability, the compounds described in theExamples below are either applied to the pigments or are used fordispersing pigments in aqueous coating systems. The coating systemschosen are aqueous polyacrylate, polyester and polyurethane systems. Theperformance characteristics (color strength, shade, transparency) of thebaking enamels produced with these coatings are tested. To evaluate thecoloristic criteria, the dilute full shade coatings are applied eitherwith a hand coater (coil coater, 24 μm wet film thickness) totransparent polyester film or with a film coater (coil film coater, 15μm wet film thickness) to contrast cardboard. The rheology was assessedvisually on the basis of the stock pastes after dispersion.

The following five-stage scale was used as a basis:

5: low viscosity

4: fluid

3: viscous

2: slightly set

1: completely set

After dilution of the mill base to the final pigment concentration, theviscosity (visc) can be determined using a Rossmann visco-spatula, Type301 from Erichsen, Iserlohn. Before the coating process, the desiredviscosity was set so that it corresponded to a certain efflux time inthe Ford cup (nozzle of 4 mm diameter), stated in seconds (s).

The color strength and shade were evaluated on the basis of whitereductions with TiO₂ or of metallic blends with aluminum.

The coloristic evaluation was carried out on the basis of the 6-stageevaluation scale stated below:

1: very little

2: slight

3: marked

4: distinct

5: significant

6: considerable

The gloss measurements were carried out at an angle of 20° according toDIN 67,530 (ASTMD 523) using a "multi-gloss" gloss meter fromByk-Mallinckrodt, Wesel. The gloss values stated in the Examples aredimensionless reflectance values. In the Preparation and Use Examplesbelow, parts relate to parts by weight and percentages are percentagesby weight. The abbreviations used have the following meanings:

"FS 3% P" means "Full shade 3% pigment content".

"1:10 TiO₂ " means "Mixture of 1 part of colored pigment and 10 parts oftitanium dioxide white pigment".

"50:50 Met" means "Mixture of 50 parts of colored pigment and 50 partsof aluminum pigment".

"D water" means "Demineralized water".

SYNTHESIS EXAMPLES

1) For the synthesis of the compound of formula IV in which X=--NH--CH₂--CH₂ --CH₂ --N(C₂ H₅)₂, Y¹ =Y₂ =--NH--C₆ H₄ --SO₃ H, Z=--NH--CH₂ --CH₂--NH-- and m=2, 17.3 parts of sulfanilic acid were added to 400 parts ofa water/ice mixture which contained 0.2 part of a sulfonated fatty acidderivative and 18.5 parts of cyanuric chloride, in stirred vessel (A),at 0° to 5° C., and the pH was kept at 6 to 9 by adding 0.2 normal NaOHsolution. After the addition of the alkali, stirring was continued forabout one hour at 0° to 5° C. Thereafter, 13.0 parts ofdiethylaminopropylamine were added at about 40° C. and the pH was keptat 6 to 9 by adding 0.2 normal NaOH solution. After the addition of thealkali, stirring was continued for about one hour at about 40° C. Instirred vessel (B), 17.3 parts of sulfanilic acid were added to 400parts of a water/ice mixture which contained 0.2 part of a sulfonatedfatty acid derivative and 18.5 parts of cyanuric chloride, at 0° to 5°C., and the pH was kept at 6 to 9 by adding 0.2 normal NaOH solution.After the addition of the alkali, stirring was continued for about onehour at 0° to 5° C. Thereafter, 3.0 parts of diaminoethane were added atabout 40° C., and the pH was kept at 6 to 9 by adding 0.2 normal NaOHsolution. After the addition of the alkali, stirring was continued forabout one hour at 40° C. The content of the stirred vessel (B) was thenadded to stirred vessel (A), and 6.0 parts of diaminoethane were addedat 80° C. and the pH was kept at 6 to 9 by adding 0.2 normal NaOHsolution. After the addition of the alkali, stirring was continued forabout a further five hours at 95° C. After the reaction mixture hadcooled at room temperature, the pH was adjusted to 1.5 with concentratedhydrochloric acid and the precipitate formed was filtered off and dried.

IR (KBr, cm⁻¹) 3300, 3100, 1630, 1590, 1550, 1500, 1220, 1170, 1030,1000

2) For the synthesis of the compound of the formula IV in whichX=--NH--CH₂ --CH₂ --CH₂ --imidazolyl, Y¹ =--NH--CH₂ --CH₂ --SO₃ H, Y²=--NH--CH₂ --CH₂ --COOH, Z=--NH--C₆ H₄ --NH-- and m=2, 25.0 parts oftaurine were added to 400 parts of water/ice mixture which contained 0.4part of a sulfonated fatty acid derivative and 36.9 parts of cyanuricchloride, in stirred vessel (A) at 0° to 5° C., and the pH was kept at 6to 9 by adding 0.2 normal NaOH solution. After the addition of thealkali, stirring was continued for about one hour at 0° to 5° C.Thereafter, 25.0 parts of N-(3-aminopropyl)-imidazole, dissolved in 50parts of water, were added at about 40° C. and the pH was kept at 6 to 9by adding 0.2 normal NaOH solution. After the addition of the alkali,stirring was continued for about one hour. In stirring vessel (B), 17.8parts of β-alanine, dissolved in 100 parts of water, were added to 400parts of a water/ice mixture which contained 0.4 part of a sulfonatedfatty acid derivative and 36.9 parts of cyanuric chloride, at 0° to 5°C., and the pH was kept at 6 to 9 by adding 0.2 normal NaOH solution.After the addition of the alkali, stirring was continued for about onehour at 0° to 5° C. Thereafter, 32.4 parts of p-phenylenediamine wereadded at about 40° C. and the pH was kept at 6 to 9 by adding 0.2 normalNaOH solution. After the addition of the alkali, stirring was continuedfor about one hour at about 40° C.

The content of the stirred vessel (B) was then added to stirred vessel(A) and, at about 80° C., the pH was kept at 6 to 9 by adding 0.2 normalNaOH solution. After the addition of the alkali, stirring was continuedfor about a further five hours at about 95° C. After the reactionmixture had cooled to room temperature, the pH was adjusted to 1.5 withconcentrated hydrochloric acid and the precipitate formed was filteredoff and dried.

IR (KBr, cm⁻¹) 3300, 3100, 1630, 1570, 1500, 1410, 1220, 1160, 1030

EXAMPLES 3-8

The following compounds of the formula IV having the substituents X, Y¹,Y² and Z were reacted according to Examples 1 and 2:

    __________________________________________________________________________    No.                                                                              X                 Y.sup.1, Y.sup.2 each                                                                      Z          m                                __________________________________________________________________________    3  --NH--(CH.sub.2).sub.3 --N(C.sub.2 H.sub.5).sub.2                                               --NH--C.sub.6 H.sub.4 --SO.sub.3 H                                                         --NH--C.sub.6 H.sub.4 --NH--                                                             2                                4  --NH--(CH.sub.2).sub.3 --N(C.sub.2 H.sub.5).sub.2                                               --NH--C.sub.6 H.sub.4 --SO.sub.3 H                                                         --NH--C.sub.6 H.sub.4 --NH--                                                             5                                5  --NH--(CH.sub.2).sub.3 --CH(CH.sub.3)N(C.sub.2 H.sub.5).sub.2                                   --NH--CH.sub.2 CH.sub.2 --SO.sub.3 H                                                       --NH--C.sub.6 H.sub.4 --NH--                                                             5                                6  --NH--(CH.sub.2).sub.3 --N(C.sub.2 H.sub.5).sub.2                                               --NH--CH.sub.2 --CH.sub.2 --SO.sub.3 H                                                     --NH--C.sub.6 H.sub.4 --NH--                                                             2                                7  --NH--(CH.sub.2).sub.3 --N(C.sub.2 H.sub.5).sub.2                                               --NH--CH.sub.2 --CH.sub.2 --SO.sub.3 H                                                     --NH--C.sub.6 H.sub.4 --NH--                                                             2                                8  -- NH--(CH.sub.2).sub.3 -imidazolyl                                                             --NH--C.sub.6 H.sub.4 --COOH                                                               --NH--C.sub.6 H.sub.4 --NH--                                                             2                                __________________________________________________________________________

    __________________________________________________________________________    Amounts of educts: (p = parts)                                                   Stirred vessel (A)                                                                      Stirred vessel (A)                                                                     Stirred vessel (B)                                                                      Stirred vessel (B)                            No.                                                                              at 0 to 5° C.                                                                    at 40° C.                                                                       at 0 to 5° C.                                                                    at 40° C.                                                                       at 80° C.                     __________________________________________________________________________    3  18.5 p. of cyanuric                                                                     13.0 p. of diethyl-                                                                    18.5 p. of cyanuric                                                                     5.4 p. of p-phenyl-                                                                    10.8 p. of p-                           chloride  aminopropylamine                                                                       chloride  enediamine                                                                             phenylenediamine                        17.3 p. of sulfa-  17.3 p. of sulfa-                                          nilic acid         nilic acid                                              4  11.1 p. of cyanuric                                                                     7.8 p. of diethyl-                                                                     27.7 p. of cyanuric                                                                     6.5 p. of p-phenyl-                                                                    13.0 p. of p-                           chloride  aminopropylamine                                                                       chloride  enediamine                                                                             phenylenediamine                        10.4 p. of sulfa-  26.0 p. of sulfa-                                          nilic acid         nilic acid                                              5  18.5 p. of cyanuric                                                                     15.8 p. of N,N-di-                                                                     46.1 p. of cyanuric                                                                     21.6 p. of p-                                                                          10.8 p. of p-                           chloride  ethylamino-4-                                                                          chloride  phenylenediamine                                                                       phenylenediamine                        12.5 p. of taurine                                                                      aminopentane                                                                           31.3 p. of taurine                                      6  20.3 p. of cyanuric                                                                     13.0 p. of diethyl-                                                                    20.3 p. of cyanuric                                                                     5.4 p. of p-phenyl-                                                                    10.8 p. of p-                           chloride  aminopropylamine                                                                       chloride  enediamine                                                                             phenylenediamine                        12.5 p. of taurine 12.5 p. of taurine                                      7  18.5 p. of cyanuric                                                                     13.0 p. of diethyl-                                                                    18.5 p. of cyanuric                                                                     9.4 p. of 2,5-di-                                                                      18.8 p. of di-                          chloride  aminopropylamine                                                                       chloride  aminobenzene-                                                                          aminobenzene-                           12.5 p. of taurine 12.5 p. of taurine                                                                      sulfonic acid                                                                          sulfonic acid                        8  18.5 p. of cyanuric                                                                     12.5 p. of N-(3-                                                                       18.5 p. of cyanuric                                                                     5.4 p. of p-                                                                           10.8 p. of p-                           chloride  aminopropyl)-                                                                          chloride  phenylenediamine                                                                       phenylenediamine                        13.7 p. of p-amino-                                                                     imidazole                                                                              13.7 p. of p-amino-                                        benzoic acid       benzoic acid                                            __________________________________________________________________________

    __________________________________________________________________________    Exam-                                                                         ple    IR (KBr, cm.sup.-1)                                                    __________________________________________________________________________    3      3400, 3000, 1630, 1590, 1550, 1500, 1410, 1220, 1160, 1030, 1000       4      3400, 3000, 1630, 1590, 1550, 1490, 1410, 1220, 1160, 1030, 1000       5      3300, 3000, 1630, 1600, 1560, 1500, 1410, 1210, 1160, 1030,            6      3300, 3000,      1570, 1500, 1420, 1210, 1160, 1030,                   __________________________________________________________________________

9) For the synthesis of the compound of the formula IV havingX=--NH--CH₂ --CH₂ --CH₂ --N(C₂ H₅)₂, Y¹ =Y² =--NH--CH₂ --CH₂ -SO₃ H,Z=--NH--C₆ H₄ --NH-- and m=2, 25.0 parts of taurine were added to 400parts of a water/ice mixture which contains 0.4 part of a sulfonatedfatty acid derivative and 36.9 parts of cyanuric chloride, in a stirredvessel, at 0° to 5° C., and the pH was kept at 6 to 9 by adding 0.2normal NaOH solution. After the addition of the alkali, stirring wascontinued for two hours at 0° to 5° C. Thereafter, 13.0 parts ofdiethylaminopropylamine were added at about 40° C. and the pH was keptat 6 to 9 by adding 0.2 normal NaOH solution. After the addition of thealkali, stirring was continued for one hour at about 40° C. Thereafter,16.2 parts of p-phenylenediamine were added at about 80° C. and the pHwas kept at 6 to 9 by adding 0.2 normal NaOH solution. After theaddition of the alkali, stirring was continued for about a further onehour at 80° C. and four hours at 95° C. After the reaction mixture hadcooled to room temperature, the pH was adjusted to 1.5 with concentratedhydrochloric acid and the precipitate formed was filtered off and dried.

IR (KBr, cm⁻¹) 3400, 3000, 1750, 1630, 1500, 1430, 1210, 1160, 1030

10) Preparation of the amine salt solutions:

The dry products prepared in Examples 1 to 9 were suspended in water,and these suspensions were adjusted to a pH of 9 to 10 with amine.During this procedure, the solid substance dissolved. It was alsopossible to add the amine directly to the undried press cake afterprecipitation with acid in Examples 1 to 9, in order to prepare a clearsolution.

PREPARATION EXAMPLES FOR PIGMENT PREPARATIONS

I) 50 parts of perylene-3,4,9,10-tetracarboxylic dianhydride, in theform of a moist press cake, were introduced into 1440 parts ofdemineralized water. After the suspension had been cooled to 0° C., 75parts of a 40% strength aqueous monomethylamine solution were addeddropwise in the course of 10 minutes. Stirring was continued for afurther 15 minutes at 0° to 5° C., and a solution of 28.5 parts ofanhydrous calcium chloride in 94.6 parts of demineralized water was thenadded in the course of 15 minutes. After stirring had been carried outfor one hour at 0° to 5° C., 26.0 parts of 21% strength aqueous solutionof the end product from Example 5 were added and the suspension washeated to 80° C. and stirred for 2 hours at this temperature.Thereafter, it was cooled to 50° C. and the pH was adjusted from 8 to8.5 with 32.5 parts of concentrated formic acid. After stirring had beencarried out for 20 minutes at 50° C., the pigment preparation wasisolated, washed salt-free with water and dried. 54.8 parts of apreparation of C.I. Pigment Red 179 were obtained.

II) 50 parts of perylene-3,4,9,10-tetracarboxylic dianhydride, in theform of a moist press cake, were introduced into 1357 parts ofdemineralized water. After the suspension had been cooled to 0° C., 93parts of a 32% strength aqueous monomethylamine solution were addeddropwise in the course of 10 minutes. Stirring was carried out for afurther 15 minutes at 0° to 5° C., and a solution of 28.5 parts ofcalcium chloride in 94.6 parts of demineralized water was then added.After stirring had been carried out for one hour at 0° to 5° C., 18.0parts of 30% strength aqueous solution of the end product from Example 4were added. The suspension was heated to 80° C. and was stirred for 2hours at this temperature. Thereafter, it was cooled to 50° C. and thepH was adjusted to 8 to 8.5 with 29.9 parts of concentrated formic acid.After stirring had been continued for 30 minutes at 50° C., the pigmentpreparation was isolated, washed chloride-free with water and dried at80° C. 58.8 parts of a preparation of C.I. Pigment Red 179 wereobtained.

III) The procedure was analogous to Example I, except that 23.7 parts ofa 22.5% strength aqueous solution of the end product from Example 6 wereused instead of 26.0 parts of a 21% strength aqueous solution of the endproduct from Example 5. 57.0 parts of a preparation of C.I. Pigment Red179 were obtained. The product contained 0.4% of calcium ions.

IV) The procedure was analogous to Example II, except that 9.0 parts ofa 30% strength aqueous solution of the end product from Example 8 wereused instead of 18.0 parts of the 30% strength aqueous solution of theend product from Example 4. 57.3 parts of a preparation of C.I. PigmentRed 179 were obtained.

V) The procedure was analogous to Example II, except that 18.0 parts ofa 30% strength aqueous solution of the end product from Example 7 wereused instead of 18.0 parts of 30% strength aqueous solution of the endproduct from Example 4. 54.1 parts of a preparation of C.I. Pigment Red179 were obtained.

VI) 40 parts of C.I. Pigment Violet 23 (prepared according to BIOS960,75), which still contained 20% of the salt resulting during thesynthesis, were introduced into a stirred vessel in which 60 parts of100% pure isobutanol and 2.5 parts of 98% strength formic acid had beeninitially taken. 80 parts of isobutanol (100%) and 240 parts ofdemineralized water were added dropwise in the course of 15 hours whilestirring at 20° to 25° C. Thereafter, the isobutanol was distilled offazeotropically with steam up to a distillation temperature of 100° C.The distillation residue was filtered and the filter cake was washedsalt-free with water. 64 parts of pigment press cake were obtained andsaid press cake was stirred with 250 parts of demineralized water and 96parts of isobutanol as well as 24.0 parts of a 15% strength aqueoussolution of the end product from Example 6 in an autoclave. Thesuspension was heated at 125° C. for 3 hours. It was allowed to cool to80° C., and the isobutanol was distilled off azeotropically with steamup to a distillation temperature of 100° C. The distillation residue wasfiltered and the filter cake was washed with water and dried at 80° C.32 parts of a preparation of C.I. Pigment Violet 23 were obtained.

VII) 31.0 parts of C.I. Pigment Violet 23, which was prepared accordingto BIOS 960,75, were introduced as a moist press cake (40% strength)into 96 parts of isobutanol (100%) and 195 parts of demineralized water.2.5 parts of concentrated formic acid and 11.0 parts of NaCl were added,and the mixture was refluxed for 1 hour. It was allowed to cool to 60°C., and the pH was adjusted to 8 to 9 with dilute sodium hydroxidesolution. Thereafter, 20.7 parts of a 15% strength aqueous solution ofthe end product from Example 4 were added, the mixture was stirred for30 minutes and the isobutanol was distilled off azeotropically withsteam up to a distillation temperature of 100° C. The distillationresidue was filtered and the filter cake was washed chloride-free withwater and dried at 80° C. 31.4 parts of a preparation of C.I. PigmentViolet 23 were obtained.

VIII) 30.0 parts of C.I. Pigment Violet 23, in the form of a moist presscake (solids content 40%), were introduced into 95 parts of isobutanol(100%) and 195 parts of demineralized water, and stirring was carriedout for 1 hour to give a homogeneous mixture. 13.7 parts of a 27%strength aqueous solution of the end product from Example 6 were addedand the mixture was heated to the reflux temperature and refluxed for 1hour. Thereafter, the isobutanol was distilled off with steam. Thedistillation residue was filtered and the filter cake was washed withwater and dried at 80° C. 30.5 parts of a preparation of C.I. PigmentViolet 23 were obtained.

IX) 30 parts of C.I. Pigment Violet 23 in the form of a moist press cake(solids content 40%), were introduced into 280 parts of demineralizedwater and stirred for 15 minutes to give a homogeneous mixture. Thelatter was heated to 90° to 95° C., 13.3 parts of a 23% strength aqueoussolution of the end product from Example 7 were added and the mixturewas allowed to cool to 30° C. while stirring. After filtration anddrying at 80° C., 29.5 parts of a preparation of C.I. Pigment Violet 23were obtained.

X) 44 parts of 2,9-dimethylquinacridone (C.I. Pigment Red 122), in theform of a moist press cake (content 24.5%), were introduced into astirred vessel in which 270 parts of isobutanol (100%), 2.5 parts ofsodium hydroxide and 50 parts of demineralized water had been initiallytaken. The suspension was stirred for 15 hours at about 20° C. and thenheated at 125° C. for 3 hours in an autoclave. The isobutanol was thenremoved by steam distillation, and 25.1 parts of a 17.5% strengthaqueous solution of the end product from Example 3 were added at 50° C.to the aqueous suspension. Stirring was continued for a further 3 hoursat 20° to 25° C. Thereafter, the mixture was filtered and the filtercake was washed with water and dried at 80° C. 43.4 parts of apreparation of C.I. Pigment Red 122 were obtained.

XI) The procedure was as described in Example VIII, except that thepigment preparation was isolated by spray drying instead of byfiltration. 23 parts of a preparation of C.I. Pigment Violet 23 wereobtained.

XII) 23 parts of a copper phthalocyanine (C.I. Pigment Blue 15), in theform of a moist press cake (solids content 23.5%), were introduced into250 parts of demineralized water and stirred overnight to give ahomogeneous mixture. The latter was then heated to 80° C. and adjustedto pH 9 to 9.5 with dimethylethanolamine, and 10.2 parts of a 22%strength aqueous solution of the end product from Example 6 were added.Stirring was continued for a further 30 minutes, the mixture beingallowed to cool to room temperature. Thereafter, the mixture wasfiltered, and the filter cake was then washed with water and dried at80° C. 23.3 parts of a preparation of C.I. Pigment Blue 15 wereobtained.

USE EXAMPLES FOR PIGMENT DISPERSIONS

A) 70 parts of a milled dolomite were dispersed in 30 parts of a 22.6%strength aqueous solution of the end product from Example 6 in adissolver for 45 minutes. The addition of 6 parts of demineralized watergave a low-viscosity dispersion whose rheology was rated at mark 4,whereas the rheology of a paste obtained without the end product fromExample 6 was rated as completely set (mark 1).

B) 8.0 parts of a gas black which had been aftertreated by oxidation,had a BET specific surface area of 470 m² /g and had a pH of 2.5 inaqueous suspension were dispersed in 71.2 parts of demineralized waterby means of a dissolver for 60 minutes, with the addition of 1.8 partsof a 22% strength aqueous solution of the end product from Example 4. Afree-flowing dispersion whose rheology was rated at 4 was obtained,whereas a slightly set dispersion (mark 2) resulted when the compoundaccording to the invention was omitted.

C) 5.0 parts of the same gas black as in Example B, which had beenaftertreated by oxidation, were dispersed in 42.5 parts of a 16%strength aqueous polyurethane dispersion in the presence of 50 parts ofglass beads (diameter 1.0 mm) in a dissolver for 60 minutes, with theaddition of 2.2 parts of an aqueous solution of the end product fromExample 6 and 0.5 part of a commercial antifoam. A free-flowing, stabledispersion whose rheology was rated at 4 was obtained.

D) 41.5 parts of demineralized water were added to 50.0 parts of a 40%strength moist press cake of C.I. Pigment Violet 23, with the additionof 8.5 parts of a 22% strength aqueous solution of the end product fromExample 6. 100 parts of glass beads (diameter 1.0 mm) were added anddispersing was carried out for 60 minutes in a laboratory bead mill.After the beads had been removed by sieving, a free-flowing dispersionof C.I. Pigment Violet 23, whose rheology was rated at 5, was obtained.

E) 6.0 parts of dimethylperylimide (C.I. Pigment Red 179), 53.4 parts ofa 16% strength aqueous polyurethane dispersion and 0.6 part of acommercial antifoam were homogenized together with 2.8 parts of a 22%strength aqueous solution of the end product from Example 6 in adissolver for 15 minutes. After the addition of 100 parts of glass beads(diameter 1.0 mm), dispersing was carried out for 60 minutes in alaboratory bead mill at 40° C. A free-flowing paste (rheology 5) wasobtained which, after dilution ("thinning") with 119.2 parts of an 18%strength aqueous polyurethane resin and 20.8 parts of demineralizedwater, gave a markedly more intense coating compared with a pigment(comparison) which was dispersed without the addition of the substanceaccording to the invention.

    ______________________________________                                               FS 3% P 1:10 TiO.sub.2                                                                           50:50 Met  Visc(s)                                  ______________________________________                                        Comparison                                                                             --        --         --       2.5                                    Example E                                                                              very little                                                                             significantly                                                                            distinctly                                                                             1.0                                             more trans-                                                                             more intense                                                                             more intense                                             parent                                                               ______________________________________                                    

F) 12.0 parts of C.I. Pigment Violet 23, 47.5 parts of a 25% strengthaqueous polyurethane resin and 0.5 part of a commercial antifoam werestirred for 15 minutes in a dissolver, after the addition of 5.5 partsof a 22% strength aqueous solution of the end product from Example 6,until a homogeneous mixture was obtained, and then, after the additionof 90 parts of glass beads (diameter 1.0 mm), were milled for 60 minutesin a mini-sand mill. After the beads had been removed by sieving,thinning was effected with 330.1 parts of a 15.3% strength aqueouspolyurethane dispersion and 9.9 parts of demineralized water. Adistinctly more intense and more glossy coating was obtained with thiscoating material compared with a paste without the compound according tothe invention (comparison).

    ______________________________________                                               FS 3% P 1:10 TiO.sub.2                                                                           50:50 Met  Gloss                                    ______________________________________                                        Comparison                                                                             --        --         --       15                                     Example F                                                                              identical significantly                                                                            significantly                                                                          56                                              transparency                                                                            more intense                                                                             more intense                                    ______________________________________                                    

G) 20.0 parts of the pigment preparation of C.I. Pigment Red 179 fromExample II, 44.0 parts of demineralized water and 36.0 parts of a 27%strength aqueous polyacrylate resin were homogenized for 15 minutes bymeans of a dissolver. After the addition of 660 parts of zirconiumdioxide beads (diameter 1.0 to 1.6 mm) and a further 33.3 parts ofdemineralized water, this suspension was dispersed for 90 minutes in a0.5 1 laboratory bead mill. A 15% strength pigment paste having verygood flow properties and a long shelf life was obtained. This paste wasdiluted with an aqueous polyurethane dispersion to a pigment content of5%, and a markedly more intense and more transparent coating wasobtained therewith in comparison to a pigment which was preparedaccording to U.S. Pat. No. 4,496,731, Example 5.

H) 6.0 parts of the pigment preparation of C.I. Pigment Red 179 fromExample III, 0.5 part of a commercial antifoam and 53.5 parts of a 30%strength aqueous polyester dispersion were premixed for 15 minutes witha dissolver and, after the addition of 100 parts of glass beads(diameter 1.0 mm), dispersed for 60 minutes in a mini-sand mill at 50°C. A 10% strength pigment paste having good flow properties wasobtained. This paste was thinned with 90 parts of a 26% strength aqueouspolyester/melamine resin dispersion to a pigment content of 3%, and amarkedly more intense and more transparent coating was obtainedtherewith compared to a pigment prepared according to U.S. Pat. No.4,496,731.

J) 6.0 parts of the preparation of C.I. Pigment Red 179 from ExampleIII, 53.4 parts of a 16% strength aqueous polyurethane dispersion and0.6 part of a commercial antifoam were homogenized for 15 minutes in adissolver. After the addition of 100 parts of glass beads (diameter 1.0mm), dispersion was carried out for 60 minutes in a mini-sand mill at40° C. A paste was obtained which had better flow properties comparedwith a commercial pigment and, after thinning with 119.2 parts of an 18%strength aqueous polyurethane resin and 20.8 parts of demineralizedwater, gave a distinctly more transparent and more intense coatingcompared with pigments which were prepared according to U.S. Pat. No.4,496,731 or U.S. Pat. No. 4,189,582, and with pigment preparationscontaining additives, as described in U.S. Pat. No. 3,622,339, Example5, and U.S. Pat. No. 4,314,001, Example 3.

Flow curves were recorded using a rotary viscometer (conditions: 22° C.,stationary for 10 minutes, increase to maximum rotational frequency in 2minutes, maintaining for 1 minute and decreasing the rotationalfrequency to zero in 2 minutes) in order to compare the rheologicalbehavior of the pigment preparation according to the invention fromExample J with that of a pigment which was prepared according to U.S.Pat. No. 4,496,731, Example 5. The pigment preparation according to theinvention showed a decrease in viscosity of about 25% relative to thecomparison.

The coloristic test gave the following differences:

    __________________________________________________________________________               FS 3% P  1:10 TiO.sub.2                                                                       50:50 Met                                                                            Gloss                                       __________________________________________________________________________    Pigment with additive                                                                    --       --     --     22                                          according to U.S.                                                                        significantly                                                                          significantly                                                                        significantly                                      Pat. No. 4,314,001                                                                       more transparent                                                                       more intense                                                                         more intense                                                                         61                                          Example J  FS 3% P  1:10 TiO.sub.2                                                                       50:50 Met                                          Pigment accord-                                                                          --       --     --                                                 ing to U.S.                                                                              significantly                                                                          distinctly                                                                           distinctly                                         Pat. No. 4,496,731                                                                       more transparent                                                                       more intense                                                                         more intense                                       (Example 5)                                                                              FS 3% P  1:10 TiO.sub.2                                                                       50:50 Met                                          Example J                                                                     Pigment accord-                                                                          --       --     --                                                 ing to U.S.                                                                              distinctly                                                                             markedly                                                                             very little                                        Pat. No. 4,189,582                                                                       more transparent                                                                       more intense                                                                         more intense                                       (Example 2)                                                                   Example J                                                                     __________________________________________________________________________

Comparison of the hue angles (measured according to DIN 5033) ofdifferent pigment preparations gave the following values: pigmentpreparation containing the compound according to the invention fromExample J: 27.5 degrees, pigment preparation according to U.S. Pat. No.4,189,582, Example 2: 23 degrees, pigment preparation according to U.S.Pat. No. 4,496,731, Example 5: 21 degrees.

K) 12.0 parts of the pigment preparation of C.I. Pigment Violet 23 fromExample VII, 0.5 part of a commercial antifoam and 47.5 parts of a 20%aqueous polyurethane resin solution were dispersed for 60 minutes in amini-sand mill at 40° C. after the addition of 100 parts of glass beads(diameter 1.0 mm). A 20% strength pigment paste having very good flowproperties was obtained. This paste was thinned with 330.1 parts of a15.3% strength aqueous polyurethane dispersion and 9.9 parts ofdemineralized water to a pigment content of 3%, and a significantly moretransparent and more intense coating having higher glass was obtainedtherewith compared to an untreated pigment (comparison) and a pigmentwhich was prepared according to U.S. Pat. No. 4,253,839, Example 2.

    __________________________________________________________________________             FS 3% P  1:10 TiO.sub.2                                                                       50:50 Met                                                                            Visc(s)                                                                           Gloss                                     __________________________________________________________________________    Comparison                                                                             --       --     --     3.5 30                                        Example K                                                                              significantly                                                                          considerably                                                                         considerably                                                                         4.9 71                                                 more transparent                                                                       more intense                                                                         more intense                                                  FS 3% P  1:10 TiO.sub.2                                                                       50:50 Met                                                                            Visc(s)                                                                           Gloss                                     Pigment accord-                                                                        --       --     --     8.9 30                                        ing to U.S.                                                                            distinctly                                                                             considerably                                                                         significantly                                                                        4.9 71                                        Pat. No. 4,253,839                                                                     more transparent                                                                       more intense                                                                         more intense                                         Example K                                                                     __________________________________________________________________________     ##STR1##

We claim:
 1. A triazine compound of formula IVwherein X is a group ofthe formula IVa

    --A.sup.1 --D.sup.1 --NR.sup.1 R.sup.2                     IVa

in which A¹ is a bridge member selected from the group consisting of O,S or NR³, wherein R³ is hydrogen or a C₁ -C₂₂ -alkyl radical or a C₃-C₂₂ -alkenyl radical which is unsubstituted or substituted by an OHgroup, D¹ is an phenylene or benzylene group or a branched orstraight-chain C₂ -C₁₂ -alkylene group which may be interrupted by oneor more bridge members selected from the group A², and A², independentlyof A¹, is selected from the same group of substituents as A¹, and R¹ andR², independently of one another, are branched or straight-chain C₁ -C₂₀-alkyl groups of C₃ -C₂₀ -alkenyl groups, or in which R¹ and R²,together with the nitrogen atom, form an unsaturated or saturated five-or six-membered ring which optionally contains one or two nitrogen,atoms as further hetero atoms in the ring, or wherein X is a group ofthe formula IVb ##STR2## in which R⁴ is C₁ -C₆ -alkyl, and Y¹ and Y²,independently of one another are each a group of the formula IVc

    --A.sup.3 --D.sup.2 --E.sup.1                              IVc

in which A³ is independent of A¹ and is a bridge member selected fromthe same group of substituents as A¹, D² is independent of D¹ and isselected from the same group of substituents as D¹ or is CH₂ or a directbond, and E¹ is an anion-forming group, selected from the groups COOM,SO₃ M, OSO₃ M or OPO₃ M₂, wherein M is hydrogen, a metal, or an ammoniumion which is unsubstituted or substituted by aliphatic, aromatic oraraliphatic radicals, and Z is a group of the formula IVd

    --A.sup.4 --Z*--A.sup.4 --                                 IVd

in which A⁴ is independent of A¹ and is a bridge member selected fromthe same group of substituents as A¹ and Z* is the group CO, branched orstraight-chain C₂ -C₂₅ -alkylene, C₅ -C₆ -cycloalkylene or C₆ -C₁₄-arylene which is unsubstituted or substituted by COOM, SO₃ M, Cl, OH oralkoxy groups, in which M has the abovementioned meanings, and wherein,in the cyclic compounds, some of the carbon atoms are optionallyreplaced by the hetero atoms nitrogen, or wherein Z* is a group of theformula (IVd')-C₂ -C₃ alkylene -Z**-C₂ -C₃ -alkylene in which Z** is thegroup N-C₁ -C₂₀ -alkyl, NH or O, or wherein Z is a bridge member of theformulae IVe and IVf

    --NH--C.sub.6 H.sub.4 --A.sup.5 --C.sub.6 H.sub.4 --NH--   IVe

    --NH--C.sub.2 --C.sub.3 -alkylene--A.sup.5 --C.sub.2 --C.sub.3 -alkylene--NH --                                          IFV

in which A⁵ is a group of the formula CR⁵ R⁶, NR⁷, O, SO, SO₂ or CO, inwhich R⁵ and R⁶, independently of one another may be branched orstraight-chain C₁ -C₄ -alkyl groups or hydrogen and wherein R⁷,independently of R³, is selected from the same group of substituents asR³,or Z is any combination of the groups of the formulae IVd, IVe andIVf, and m is an integer from 1 to
 100. 2. A triazine compound of theformula IV as claimed in claim 1, whereinX is a group of the formula IVa

    --A.sup.1 --D.sup.1 --NR.sup.1 R.sup.2                     IVa

in which A¹ is a bridge member selected from the group consisting of Oor NR³, wherein R³ is hydrogen or a C₁ -C₂₂ -alkyl radical or a C₃ -C₂₂-alkyl radical which is unsubstituted or substituted by an OH group, D¹is an phenylene or benzylene group or a branched or straight-chain C₂-C₁₂ -alkylene group which are optionally interrupted by one or morebridge members selected from the group A², and A², independently of A¹,is selected from the same group of substituents as A¹, and R¹ and R²,independently of one another, are branched or straight-chain C₁ -C₂₀-alkyl groups of C₃ -C₂₀ -alkenyl groups, or in which R¹ and R²,together with the nitrogen atom, form an unsaturated or saturated five-or six-membered ring which may additionally contain one or two nitrogenatoms as further hetero atoms in the ring, or wherein X is a group ofthe formula IVb ##STR3## in which R⁴ is C₁ -C₆ -alkyl, and Y¹ and Y²,independently of one another are each a group of the formula IVc

    --A.sup.3 --D.sup.2 --E.sup.1                              IVc

in which A³ is independently of A¹ and is a bridge member selected fromthe same group of substituents as A¹, D² is independent of D¹ and isselected from the same group of substituents as D¹ of is CH₂ or a directbond, and E¹ is an anion-forming group, selected from the groups COOM orSO₃ M, wherein M is hydrogen, a metal, or an ammonium ion which isunsubstituted or substituted by aliphatic, aromatic and araliphaticradicals, and Z is a group of the formula IVd

    --A.sup.4 --Z*--A.sup.4 --                                 IVd

in which A⁴ is independent of A¹ and is a bridge member selected fromthe same group of substituents as A¹ and Z* is the group CO, NR³, inwhich R³ has the abovementioned meaning, branched or straight-chain C₂-C₂₅ -alkylene, C₅ -C₆ -cycloalkylene or phenylene, which isunsubstituted or substituted by COOM or SO₃ M, in which M has theabovementioned meanings, and wherein, in the cyclic compounds, some ofthe carbon atoms may be replaced by the hetero atoms nitrogen, or Z is acombination of the groups of the formula IVd, and m is an integer of 1to
 100. 3. A triazine compound of the formula IV as claimed in claim 1,whereinX is a group of the formula IVg ps ti --A¹ --D¹ --NR¹ R² IVgwherein A¹ is NR³, in which R³ is methyl or hydrogen, D¹ is a branchedor straight-chain C₂ -C₆ -alkylene group or a phenylene group and R¹ andR², independently of one another are branched or straight chain C₁ -C₆alkyl groups, or in which R¹ and R², together with the nitrogen atom,form an unsaturated or saturated five- or six-membered ring which mayadditionally contain one or two nitrogen atoms as further hetero atomsin the ring, and Y¹ and Y², independently of one another are each agroup of the formula IVh

    A.sup.3 --D.sup.2 --E.sup.1                                IVh

wherein A³ is NR³, in which R³ is methyl or hydrogen and D² isindependent of D¹ and is selected from the same group of substituents asD¹ or is CH₂ or a direct bond, and E¹ is an anion-forming group selectedfrom the groups COOM or SO₃ M, wherein M is hydrogen, a metal or anammonium ion which is unsubstituted or substituted by aliphatic,aromatic and araliphatic radicals, and Z is a group of the formula --A⁴--Z*--A⁴, wherein A⁴ is NR³, in which R³ is methyl or hydrogen and Z* isthe group C₂ -C₆ -alkylene or phenylene, which is unsubstituted orsubstituted by COOM or SO₃ M, in which M has the abovementionedmeanings, or wherein Z* is a group of the IVi.

    --C.sub.2 --C.sub.3 -alkylene-Z**--C.sub.2 --C.sub.3 -alkylene IVi

in which Z** is the group N--C₁ -C₂₀ -alkyl, NH or O, and m is aninteger of from 1 to
 30. 4. A triazine compound of the formula IV asclaimed in claim 1, wherein M is an alkali metal or the stoichiometricamount of an alkaline earth metal.
 5. Method of using a compound asclaimed in claim 1 as pigments.